CN107973759B - Preparation method of acryloyl morpholine - Google Patents
Preparation method of acryloyl morpholine Download PDFInfo
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- CN107973759B CN107973759B CN201711372683.3A CN201711372683A CN107973759B CN 107973759 B CN107973759 B CN 107973759B CN 201711372683 A CN201711372683 A CN 201711372683A CN 107973759 B CN107973759 B CN 107973759B
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- morpholine
- dioctadecylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
Abstract
The invention provides a preparation method of acryloyl morpholine, in particular to a method for preparing acryloyl morpholine by a cracking method, which adopts dioctadecyl amine as a raw material to react with acrylic ester, the preparation condition is mild, and the purification process is simple; the product is easy to purify and not easy to generate polymerization phenomenon; volatile amine generated by cracking is effectively avoided in the product purification process, and the volatile amine reacts with the product to generate intermediate impurities; the cracking efficiency and the product yield are improved; the amine generated by cracking is not easy to volatilize and easy to recycle, thereby saving the cost.
Description
Technical Field
The invention relates to a preparation method of acryloyl morpholine, in particular to a method for preparing acryloyl morpholine by a cracking method.
Background
N-acryloyl morpholine is a functional monomer and a reactive diluent with excellent performance, and is commonly used as a reaction diluent of ultraviolet curing resin. Due to the double bond and the morpholine group, the epoxy resin has active chemical properties (high sensitivity), does not generate any pungent smell (extremely low smell), and has the characteristics of low viscosity, quick curing, strong diluting capability and the like. The UV and EB curing resin modified by the N-acryloyl morpholine has low hygroscopicity, and has good characteristics of acid resistance, alkali resistance and solvent resistance. The product modified by taking N-acryloyl morpholine as a raw material is applied to the fields of oil field additives, printing ink additives, papermaking additives, adhesives and the like. Poly-N-acryloyl morpholine (PACM) synthesized by taking acryloyl morpholine as a monomer has a hydrophilic morpholine group and a hydrophobic carbon chain structure in the molecular structure, so that the poly-N-acryloyl morpholine is soluble in water and most of organic solvents, has excellent amphipathy and biocompatibility, can control the drug release speed of the drug in vivo by adjusting the molecular weight, and is a good drug controlled release carrier. N-acryloyl morpholine is the best choice for replacing toxic acrylamide monomer and polymerization product thereof in some water treatment fields due to no toxicity.
The synthesis method of N-acryloyl morpholine mainly comprises 2 methods:
one is prepared by preparing acryloyl chloride from acrylic acid, followed by reaction with morpholine; the method disclosed by US2683703, US4959364, CN 1345302, He Zhang Yu and the like, the collection of the collected discourse of the twenty-fifth annual meeting of the chemical society of Gansu province and the like has the advantages of simple process flow and the defects of more by-products, low yield, high corrosivity and difficult separation.
The other is prepared by cracking 3-substituent propionyl morpholine, and the structure of the 3-substituent propionyl morpholine is as follows:
JPH111000375 discloses the use of 3-morpholinopropionyl morpholine by vacuum cleavage. Under the action of acid catalyst, the N-acryloyl morpholine is synthesized by vacuum thermal cracking, but the yield is 29 percent at most.
On the basis, patent CN2014100280873 is improved, and 3-morpholinyl is changed into diethylamino to solve the problem that 3-morpholinyl propionyl morpholine is not easy to separate from the product acryloyl morpholine.
However, in tests, 3-substituent propionyl morpholine has a very serious problem in the cracking process, the cracking process is vacuum thermal cracking, and when the product is purified, the product acryloyl morpholine and volatile amine (morpholine and diethylamine) react to generate 3-substituent propionyl morpholine, so that the product contains 3-substituent propionyl morpholine, and the purity of the product is influenced and is not easy to purify again.
Disclosure of Invention
The invention aims to provide a novel method for preparing N-acryloyl morpholine, which can overcome various defects in the prior art and has the advantages that: firstly, dioctadecylamine is adopted as a raw material to react with acrylic ester, the preparation condition is mild, and the purification process is simple; secondly, the product is easy to purify and does not generate polymerization; third, volatile amine generated by cracking is avoided in the product purification process, and the product reacts with the volatile amine to generate intermediate impurities; and fourthly, the amine generated by cracking is not easy to volatilize and easy to recycle, so that the cost is saved.
The preparation method of acryloyl morpholine provided by the invention comprises the following steps:
1) taking dioctadecyl amine and acrylic ester as raw materials, adding a proper amount of polymerization inhibitor and catalyst, and carrying out Michael addition reaction;
2) adding morpholine and a catalyst into the obtained 3- (N, N-dioctadecylamine) propionate in sequence, heating for reaction, and recovering the solvent and the morpholine after the reaction is finished to obtain 3- (N, N-dioctadecylamine) propionylmorpholine;
3) adding a proper amount of polymerization inhibitor into 3- (N, N-dioctadecylamine) propionyl morpholine, carrying out vacuum cracking, and simultaneously rectifying to obtain a product;
wherein the catalyst in the step 1) is selected from potassium carbonate, sodium carbonate, potassium tert-butoxide and sodium tert-butoxide, and the dosage of the catalyst is 0.1-50% of the amount of the dioctadecylamine;
step 2) the catalyst is selected from alkali metal alcoholates, preferably sodium methylate.
In the preparation method of acryloyl morpholine, raw material acrylic ester is not particularly limited, methyl acrylate, ethyl acrylate and propyl acrylate are preferred, and methyl acrylate is most preferred because of the advantage of price on one hand, and the by-product methanol is low in boiling point and easy to remove on the other hand. Taking methyl acrylate as an example, the reaction process can be simplified as follows:
the preparation method of acryloyl morpholine is characterized in that the used polymerization inhibitor is selected from hydroquinone, benzoquinone, phenothiazine, nitrobenzene, picric acid, p-hydroxyanisole and butyl catechol, and the dosage of the polymerization inhibitor is 0.1-10% of the mass of acrylic ester.
The preparation method of acryloyl morpholine provided by the invention is characterized in that the dosage of the dioctadecyl amine and the acrylic ester in the step 1) is selected from the ratio of the amount of the dioctadecyl amine to the amount of the acrylic ester: 1.0 (1.0-2.0); if other organic solvents are not used in the reaction process, the acrylate itself is used as the solvent, and the dosage of the acrylate can be 2-20 times of that of the dioctadecylamine. Other solvents which can be used are selected from dichloroethane, acetonitrile, dichloromethane, methanol, ethanol, n-hexane and the like, and preferably, the acrylate itself is used as the solvent, so that the acrylate is convenient to recycle and avoid cross contamination with other organic solvents.
The preparation method of acryloyl morpholine provided by the invention is characterized in that the dosage of morpholine in the step 2) is 1.0-2.0 times of that of dioctadecylamine.
The preparation method of acryloyl morpholine provided by the invention is characterized in that the vacuum cracking temperature in the step 3) is controlled at 140-180 ℃.
The preparation method of acryloyl morpholine provided by the invention is characterized in that amine dioctadecyl amine which is not easy to volatilize is used for protecting double bonds of acrylic ester, then amidation reaction is carried out on the acrylamide and morpholine, finally, vacuum cracking is carried out to obtain a product and dioctadecyl amine, the product is directly distilled off by steam, and the dioctadecyl amine is not easy to volatilize and remains in a reaction container. Firstly, the amine is convenient to recover and is not easy to lose; and secondly, the most important is that the product acryloyl morpholine and amine can be effectively prevented from contacting with each other again in the distillation process to react to generate the raw material 3-substituted propionyl morpholine which enters the product and is not easy to remove, so that the product purity is reduced, the performance of the acryloyl morpholine is greatly influenced in the use process, and the cracking efficiency and the product yield are improved again. The 3-substituted propionyl morpholine does not contain a double bond, so that the 3-substituted propionyl morpholine can be left as small molecules in curing or other reactions, and the risks of mobility and volatility are greatly increased. In the experimental process, the inventor finds that whether morpholine (JP 111000375) or diethylamine (CN 2014100280873) is used, in the vacuum cracking process, 3-morpholine propionyl morpholine or 3-diethylaminopropionyl morpholine are easily contained in the distilled product, and the distillation efficiency and the product purity are influenced.
The method for preparing the acryloyl morpholine by the single-vessel method has the advantages that:
1. the dioctadecylamine is adopted as a raw material to react with the acrylic ester, the preparation condition is mild, and the purification process is simple;
2. the product is easy to purify and not easy to generate polymerization phenomenon;
3. volatile amine generated by cracking is effectively avoided in the product purification process, and the volatile amine reacts with the product to generate intermediate impurities;
4. the cracking efficiency and the product yield are improved;
5. the amine generated by cracking is not easy to volatilize and easy to recycle, thereby saving the cost.
Detailed Description
The invention will be further illustrated by the following non-limiting examples.
Example 1: preparation of acryloyl morpholine
Taking 86.1g (1.0 mol) of methyl acrylate, 104.4g (0.2 mol) of dioctadecylamine, 4.3g of p-methoxyphenol and 5.3g (0.05 mol) of sodium carbonate, heating to 50 ℃, preserving the temperature for reaction, filtering after the reaction is finished, and recovering 67.0g of methyl acrylate from the filtrate in vacuum to obtain 117.3g of white solid methyl 3- (dioctadecylamine) propionate; adding 26.1g (0.3 mol) of morpholine and 1.6g (0.03 mol) of sodium methoxide into the mixture, heating the mixture to 85-90 ℃, after the reaction is finished, regulating the pH to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 125.3g of 3- (dioctadecylamino) propionyl morpholine, adding 2.3g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying to obtain 19.2g of acryloyl morpholine, wherein the yield is 68.1%, and the purity is 99.0%. Wherein, the still residue contains not only dioctadecylamine but also 10 percent of 3- (dioctadecylamino) propionyl morpholine, and the still residue can be directly used.
Example 2: preparation of acryloyl morpholine
Taking 86.1g (1.0 mol) of methyl acrylate, 104.4g (0.2 mol) of dioctadecylamine, 4.3g of p-methoxyphenol and 2.9 (0.03 mol) of sodium tert-butoxide, heating to 50 ℃, preserving the temperature for reaction, filtering after the reaction is finished, and recovering 65.9g of methyl acrylate from the filtrate in vacuum to obtain 117.9g of white solid methyl 3- (dioctadecylamine) propionate; adding 26.1g (0.3 mol) of morpholine and 1.6g (0.03 mol) of sodium methoxide into the mixture, heating the mixture to 85-90 ℃, after the reaction is finished, regulating the pH to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 124.9g of 3- (dioctadecylamino) propionyl morpholine, adding 2.3g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying to obtain 19.5g of acryloyl morpholine, wherein the yield is 69.1%, and the purity is 98.8%.
Example 3: preparation of acryloyl morpholine
Taking the residue obtained in the step of cracking and rectifying in the example 1, adding 86.1g (1.0 mol) of methyl acrylate, 4.3g of p-methoxyphenol and 5.3g (0.05 mol) of sodium carbonate, heating to 50 ℃, keeping the temperature for reaction, filtering after the reaction is finished, and recovering 66.0g of methyl acrylate from the filtrate in vacuum to obtain 120.3g of a white solid crude product of the methyl 3- (dioctadecylamino) propionate; adding 26.1g (0.3 mol) of morpholine and 1.6g (0.03 mol) of sodium methoxide into the mixture, heating the mixture to 85-90 ℃, after the reaction is finished, regulating the pH to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 129.3g of 3- (dioctadecylamino) propionyl morpholine, adding 2.3g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying to obtain 19.9g of acryloyl morpholine, wherein the yield is 70.6%, and the purity is 99.2%. Wherein, the kettle residue contains 9 percent of 3- (dioctadecylpropionyl morpholine) besides dioctadecylamine, and the kettle residue can be directly used.
Example 4: preparation of acryloyl morpholine
Taking the residue obtained in the step of cracking and rectifying in the embodiment 3, adding 86.1g (1.0 mol) of methyl acrylate, 4.3g of p-methoxyphenol and 5.3g (0.05 mol) of sodium carbonate, heating to 50 ℃, keeping the temperature for reaction, filtering after the reaction is finished, and recovering the methyl acrylate from the filtrate in vacuum to obtain 119.5g of a white solid methyl 3- (dioctadecyl) propionate crude product; adding 26.1g (0.3 mol) of morpholine and 1.6g (0.03 mol) of sodium methoxide into the mixture, heating the mixture to 85-90 ℃, after the reaction is finished, regulating the pH to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 123.3g of 3- (dioctadecylamino) propionyl morpholine, adding 2.3g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying to obtain 19.0g of acryloyl morpholine, wherein the yield is 67.4 percent and the purity is 99.5 percent. Wherein, the kettle residue contains 12 percent of 3- (dioctadecylpropionyl morpholine) besides dioctadecylamine, and the kettle residue can be directly used.
Example 5: preparation of acryloyl morpholine
Taking 60ml of dichloromethane, 20.7g (0.24 mol) of methyl acrylate, 104.4g (0.2 mol) of dioctadecylamine, 2.3g of p-methoxyphenol and 2.9 (0.03 mol) of sodium tert-butoxide, heating to 50 ℃, carrying out heat preservation reaction, filtering after the reaction is finished, and recovering methyl acrylate and dichloromethane serving as a solvent from filtrate in vacuum to obtain white solid methyl 3- (dioctadecylamine) propionate; adding 26.1g (0.3 mol) of morpholine and 1.6g (0.03 mol) of sodium methoxide into the mixture, heating the mixture to 85-90 ℃, after the reaction is finished, regulating the pH value to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 3- (dioctadecylpropionyl morpholine), adding 2.3g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying 18.5g of acryloyl morpholine, wherein the yield is 65.8 percent and the purity is 99.0 percent.
Example 6: preparation of acryloyl morpholine
Taking 17.2g (0.2 mol) of methyl acrylate, 21.9g (0.3 mol) of diethylamine and 0.86g of p-methoxyphenol, heating to 65-70 ℃, preserving the temperature for reaction, and removing low-boiling-point substances after the reaction is finished to obtain 3- (diethylamino) methyl propionate; adding 18.3g (0.21 mol) of morpholine and 4.7g (0.87 mol) of sodium methoxide into the mixture, heating the mixture to 80-85 ℃, after the reaction is finished, regulating the pH value to be neutral by hydrochloric acid, removing low-boiling components, then adding dichloroethane for dissolving, filtering out insoluble substances, then recovering the dichloroethane to obtain 3- (diethylamino) propionyl morpholine, adding 0.86g of p-methoxyphenol, then carrying out vacuum cracking, and rectifying 11.8g of acryloyl morpholine, wherein the yield is 41.8 percent and the purity is 53 percent.
Example 7: preparation of acryloyl morpholine
Taking 17.2g (0.2 mol) of methyl acrylate, 43.5g (0.3 mol) of morpholine and 0.86g of p-methoxyphenol, heating to 65-70 ℃, carrying out heat preservation reaction, adding 4.7g (0.87 mol) of sodium methoxide after the reaction is finished, heating to 80-85 ℃, continuing the heat preservation reaction, adjusting the pH to be neutral by using hydrochloric acid after the reaction is finished, removing low-boiling components, adding dichloroethane for dissolving, filtering out insoluble substances, recovering the dichloroethane to obtain 3- (morpholinyl) propionyl morpholine, adding 0.86g of p-methoxyphenol, carrying out vacuum cracking, and rectifying 8.46g of acryloyl morpholine, wherein the yield is 30.0%, and the purity is 49%.
Claims (6)
1. A preparation method of acryloyl morpholine comprises the following steps:
1) taking dioctadecyl amine and acrylic ester as raw materials, adding a proper amount of polymerization inhibitor and catalyst, and carrying out Michael addition reaction;
2) adding morpholine and a catalyst into the obtained 3- (N, N-dioctadecylamine) propionate in sequence, heating for reaction, and recovering the solvent and the morpholine after the reaction is finished to obtain 3- (N, N-dioctadecylamine) propionylmorpholine;
3) adding a proper amount of polymerization inhibitor into 3- (N, N-dioctadecylamine) propionyl morpholine, carrying out vacuum cracking, and simultaneously rectifying to obtain a product;
wherein the catalyst in the step 1) is selected from potassium carbonate, sodium carbonate, potassium tert-butoxide and sodium tert-butoxide, and the dosage of the catalyst is 0.1-50% of that of the dioctadecylamine;
step 2) the catalyst is selected from sodium methoxide;
and 3) controlling the vacuum cracking temperature to be 140-180 ℃.
2. The process for preparing acryloyl morpholine according to claim 1, wherein the polymerization inhibitor is selected from hydroquinone, benzoquinone, phenothiazine, nitrobenzene, picric acid, p-hydroxyanisole, butyl catechol.
3. The method for preparing acryloyl morpholine according to claim 1, characterized in that the amount of polymerization inhibitor used is 0.1-10% of the mass of acrylic ester.
4. The method for preparing acryloylmorpholine according to claim 1, wherein the amount of dioctadecylamine and acrylic ester used in step 1) is the ratio of the amount of dioctadecylamine to the amount of acrylic ester: 1.0 (1.0-2.0); if other organic solvents are not used in the reaction process, the acrylate is used as the solvent, and the dosage of the acrylate is 2-20 times of that of the dioctadecylamine.
5. The process for preparing acryloylmorpholine according to claim 1, wherein step 1) is carried out in dichloroethane, acetonitrile, dichloromethane, methanol, ethanol or n-hexane.
6. The method for preparing acryloyl morpholine according to claim 1, wherein the amount of morpholine used in step 2) is 1.0-2.0 times that of dioctadecylamine.
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